Energy polymerizable compositions containing organometallic initiators

ABSTRACT

An energy polymerizable composition and process therefore, comprising a cationically polymerizable material and a catalytically effective amount of an ionic salt of an organometallic complex cation as polymerization initiator, said ionic salt of an organometallic complex cation being capable of adding an intermediate strengeth nucleophile or upon photolysis capable of liberating at least one coordination site, said metal in said organometallic complex cation being selected from elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB are disclosed. Certain of the organometallic metallic polymerization initiators are novel cationic salts.

This is a divisional application of U.S. Ser. No. 06/443,660, filed Nov.22, 1982, now U.S. Pat. No. 5,089,536.

TECHNICAL FIELD

The present invention relates to a process for the polymerization ofcationically-sensitive materials employing as polymerization initiator acertain class of ionic organometallic compounds. In another aspect, itrelates to polymerizable compositions containing cationically-sensitivematerials and organometallic complex compounds. In a further aspect, itrelates to certain organometallic polymerization initiators.

BACKGROUND ART

The prior art describes various processes for the initiation of cationicpolymerization, particularly the polymerization of epoxy materials. Itis known to cure epoxy materials by use of curing additives such aspolybasic anhydrides, organic peroxides, and quinone. It is furtherknown that a metallocene, such as ferrocene, can be used as a curingaccelerator for epoxy materials and is described in U.S. Pat. No.3,705,129. U.S. Pat. Nos. 3,709,861 and 3,714,006 describe the use ofcyclopentadienylmanganese tricarbonyl for the acceleration of thelight-catalyzed reaction between polyepoxides and acid anhydrides orpolymercaptans. U.S. Pat. No. 3,867,354 discloses the use of bis- andtris-salicylic acid complexes of chromium(III) to catalyze the reactionbetween epoxides and carboxylic acids, and U.S. Pat. No. 4,237,272relates to the use of transition metal complexes (chromium, manganese,iron, etc.) of acetylacetonate type ligands to accelerate the thermallyinitiated reaction of carboxylic acid group-containing polymers withpolyepoxides. Each of the above-mentioned patents teaches theacceleration of the reaction between polyepoxides and polyfunctionalcuring additives, but they do not teach the polymerization of epoxidegroup-containing compositions not containing a curing additive.

The polymerization of cationically-polymerizable materials, specificallyepoxide group-containing materials, in the absence of curing additivesis, however, well known. Among such processes are those in which thepolymerization catalyst (also called sensitizer or initiator) is (1) aradiation-sensitive onium salt of a Lewis acid (e.g. diazonium salts asis described in U.S. Pat. No. 3,794,576 and U.S. Pat. No. 4,080,274;halonium salts as is disclosed in U.S. Pat. No. 4,026,705; and the oniumsalts of Group VIA elements, particularly the sulfonium salts, as aredisclosed in U.S. Pat. No. 4,058,400); (2) a dicarbonyl chelate compoundof a Group IIIA-VA element as is disclosed in U.S. Pat. No. 4,086,091;(3) a silver salt which is used for the polymerization oftetrahydrofuran as is described by Woodhouse, et al., J. Am. Chem. Soc.100, 996 (1978); and (4) titanocene dichloride which is used for thepolymerization of epichlorohydrin and 2-chloroethylvinyl ether as isdescribed by Kaerijama et al., J. Polym. Sci., Chem. Ed. 10, 2833 (1972)and Ibid, 14, 1547 (1976). Compositions containing the above-mentionedcatalysts are unsatisfactory because without the addition of opticalsensitizers they are limited to ultraviolet radiation forpolymerization. Furthermore, the dicarbonyl chelates are moisturesensitive and the titanocene dichloride requires a co-catalyst.

DISCLOSURE OF THE INVENTION

The present invention provides a process for the polymerization ofcationically-sensitive materials utilizing as catalyst a cationiccompound which is a salt of an organometallic complex cation. Byselection of the metal and ligands in the organometallic complex and thecounterion used, the relative thermal stability and wavelength ofsensitivity (from 200 to 600 nm) can be adapted for variousapplications.

In accordance with the present invention there is providedenergy-curable compositions comprising:

a) a cationically-polymerizable material and

b) a catalytically-effective amount of an ionic salt of anorganometallic complex cation sufficient to effect polymerization, saidionic salt of an organometallic complex cation being capable of addingan intermediate strength nucleophile such as triphenylphosphine or uponphotolysis capable of liberating at least one coordination site, saidmetal of said organometallic complex cation being selected from elementsof Periodic Groups IVB, VB, VIB, VIIB, and VIIIB.

There is also provided a process for the polymerization of cationicallysensitive material comprising the steps of:

a) mixing the cationically-sensitive material with acatalytically-effective amount of the ionic salt of an organometalliccomplex cation, thereby forming a mixture, and

b) allowing the mixture to polymerize or adding energy to the mixture toeffect polymerization thereof.

As used in this application:

"catalytically effective amount" means a quantity sufficient to effectpolymerization of the cationically-polymerizable material at least to adegree to increase the viscosity of the composition, and

"intermediate strength nucleophile" means a nucleophile intermediate instrength between hydride and chloride, e.g., trialkyl- andtriarylphosphines, trialkyl- and triarylphosphites, pyridines, andanilines.

DETAILED DESCRIPTION OF THE INVENTION

The ionic salts of the organometallic complex cations useful in thecompositions and processes of the invention are compounds having theformula:

    [L.sup.1a)(L.sup.2a)(L.sup.3a)M.sup.a ].sub.g ][(L.sup.1b)(L.sup.2b)(L.sup.3b)M.sup.b ].sub.h [(L.sup.1c) (L.sup.2c)(L.sup.3c)M.sup.c ].sub.j [(L.sup.1d)(L.sup.2d)(L.sup.3d)M.sup.d ].sub.k (L.sup.4)(L.sup.5)(L.sup.6).sup.+e X.sub.f        I

wherein

M^(a), M^(b), M^(c), and M^(d) represent metal atoms which may be thesame or different selected from the elements of Periodic Groups IVB, VB,VIB, VIIB, and VIIIB;

with the proviso that Formula I can represent a mononuclear, binuclear,trinuclear, or tetranuclear complex compound comprising M^(a), M^(a)M^(b), M^(a) M^(b) M^(c), or M^(a) M^(b) M^(c) M^(d) respectively withtheir attendent ligands, L;

each L^(1a), L^(1b), L^(1c), and L^(1d) represents none, or 1, 2, or 3ligands contributing π-electrons that can be the same or differentligand selected from substituted and unsubstituted acyclic and cyclicunsaturated compounds and groups and substituted and unsubstitutedcarbocyclic aromatic and heterocyclic aromatic compounds, each capableof contributing two to twelve π-electrons to the valence shell of M^(a),M^(b), M^(c), and M^(d), respectively;

each L^(2a), L^(2b), L^(2c), and L^(2d) represents none, or 1 to 6ligands contributing an even number of σ-electrons that can be the sameor different selected from mono-, di-, and tri-dentate ligands, eachdonating 2, 4, or 6 σ-electrons to the valence shell of M^(a), M^(b),M^(c), and M^(d), respectively;

each L^(3a), L^(3b), L^(3c), and L^(3d) represents none, 1, or 2 ligandscontributing one o-electron each to the valence shell of M^(a), M^(b),M^(c), and M^(d), respectively;

L⁴ represents none, or 1 to 6 bridging ligands containing σ-electronsthat can be the same or different ligand selected from substituted andunsubstituted acyclic and cyclic unsaturated compounds and groups andsubstituted and unsubstituted carbocyclic aromatic and heterocyclicaromatic compounds, each capable of acting as a bridging ligandcontributing 2 to 24 π-electrons to the valence shells of two or moremetal atoms M^(a), M^(b), M^(c), or M^(d) simultaneously;

L⁵ represents none, or 1 to 12 bridging ligands contributing an evennumber of σ-electrons that can be the same or different selected frommono-, di-, and tri-dentate ligands, each donating 2, 4, or 6σ-electrons to the valence shells of two or more metal atoms M^(a),M^(b), M^(c), or M^(d) simultaneously;

L⁶ represents none or 1 to 12 bridging ligands contributing 1, 2, 3, or4 σ-electrons to the valence shells of two or more metal atoms M^(a),M^(b), M^(c), or M^(d) simultaneously;

with the proviso that the total electronic charge contributed to M^(a),M^(b), M^(c), and M^(d) by the ligands L^(1a), L^(2a), L^(3a), L^(1b),L^(2b), L^(3b), L^(1c), L^(2c), L^(3c), L^(1d), L^(2d), L^(3d), L⁴, L⁵,and L⁶ plus the sum of ionic charge on M^(a), M^(b), M^(c), and M^(d),results in a residual net positive charge of e to the complex;

e is an integer having a value of 1, 2, or 3, the residual electricalcharge of the complex cation;

X is a halogen-containing complex anion of a metal or metalloid;

f is an integer of 1 to 3, the number of complex anions required toneutralize the charge e on the complex cation; and

g, h, j, and k independently are 0 or 1, with at least one of them,being equal to 1.

By Periodic Group IVB is meant the elements Ti, Zr, and Hf.

By Periodic Group VB is meant the elements V, Nb, and Ta.

By Periodic Group VIB is meant the elements Cr, Mo, and W.

By Periodic Group VIIB is meant the elements Mn, Tc, and Re, and

By Periodic Group VIIIB is meant the elements Fe, Ru, Os, Co, Rh, Ir,Ni, Pd, and Pt.

In a preferred composition of the invention, the salts of theorganometallic cation have the formula:

    [(L.sup.7)(L.sup.8)M.sup.m ].sup.+e X.sub.f                II

wherein

M^(m) represents a metal selected from elements of the Periodic GroupsIVB, VB, VIB, VIIB, and VIIIB;

L⁷ represents none, one or two ligands contributing π-electrons that canbe the same or different ligand selected from the same group of ligandsfrom which L^(1a), L^(1b), L^(1c), and L^(1d) ligands of Formula I isselected;

L⁸ represents none or 1 to 6 ligands contributing an even number ofσ-electrons that can be the same or different ligand selected from thesame group of ligands from which L^(2a), L^(2b), L^(2c), and L^(2d)ligands of Formula I is selected;

with the proviso that the total electronic charge contributed to M^(m)by L⁷ and L⁸ plus the ionic charge on Mm results in a residual netpositive charge of e to the complex; and e, f, and X have the samedefinition as given in Formula I.

In a most preferred composition of the invention, the salts of theorganometallic cation are novel and have the formula:

    [(L.sup.9)(L.sup.10)M.sup.p ].sup.+q Y.sub.n               III

wherein

M^(p) represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co;

L⁹ represents 1 or 2 ligands contributing x-electrons that can be thesame or different ligand selected from substituted and unsubstituted η³-allyl, η⁵ -cyclopentadienyl, and η⁷ -cycloheptatrienyl and η⁶ -aromaticcompounds selected from η⁶ -benzene and substituted η⁶ -benzenecompounds and compounds having 2 to 4 fused rings each capable ofcontributing 3 to 8 π-electrons to the valence shell of M^(p) ;

L¹⁰ represents none or 1 to 3 ligands contributing an even number ofσ-electrons that can be the same or different ligand selected fromcarbon monoxide or nitrosonium; with the proviso that the totalelectronic charge contributed to M^(p) by L⁹ and L¹⁰ plus the ioniccharge on metal M^(p) results in a net residual positive charge of q tothe complex, and

q is an integer having a value of 1 or 2, the residual electrical chargeof the complex cation;

Y is a halogen-containing complex anion selected from AsF₆ -, SbF⁶ - andSbF₅ OH-; and

n is an integer having a value of 1 or 2, the numbers of complex anionsrequired to neutralize the charge q on the complex cation.

Salts of organometallic cations having Formulas I, II, and III areradiation sensitive in addition to being thermally sensitive.

All ligands L^(1a) to L¹⁰ are well known in the art of transition metalorganometallic compounds.

Ligands L^(1a), L^(1b), L^(1c), and L^(1d) in Formula I, and L⁷ inFormula II, are provided by any monomeric or polymeric compound havingan accessible unsaturated group, i.e., an ethylenic, ##STR1## group;acetylenic, --C.tbd.C-- group; or aromatic group which have accessibleπ-electrons regardless of the total molecular weight of the compound. By"accessible", it is meant that the compound (or precursor compound fromwhich the accessible compound is prepared) bearing the unsaturated groupis soluble in a reaction medium, such as an alcohol, e.g., methanol; aketone, e.g., methyl ethyl ketone; an ester, e.g., amyl acetate; ahalocarbon, e.g., trichloroethylene; an alkane, e.g., decalin; anaromatic hydrocarbon, e.g., anisole; an ether, e.g., tetrahydrofuran;etc, or that the compound is divisible into very fine particles of highsurface area so that the unsaturated group (including aromatic group) issufficiently close to a metal atom to form a π-bond joining theunsaturated group to the metal atom. By polymeric compound, it is meant,as explained below, that the ligand can be a group on a polymeric chain.

Illustrative of ligands L^(1a), L^(1b), L^(1c), L^(1d), and L⁷ are thelinear and cyclic olefinic and acetylenic compounds having less than 100carbon atoms, preferably having less than 60 carbon atoms, and up to 10hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus,arsenic, selenium, boron, antimony, tellurium, silicon, germanium, andtin, such as, for example, ethylene, acetylene, propylene,methylacetylene, 1-butene, 2-butene, diacetylene, butadiene,1,2-dimethylacetylene, cyclobutene, pentene, cyclopentene, hexene,cyclohexene, 1,3-cyclohexadiene, cyclopentadiene, 1,4-cyclohexadiene,cycloheptene, 1-octene, 4-octene, 3,4-dimethyl-3-hexene, and 1-decene;η³ -allyl, η³ -pentenyl, norbornadiene, η⁵ -cyclohexadienyl, η⁶-cycloheptatriene, η⁸ -cyclooctatetracene, and substituted andunsubstituted carbocyclic and heterocyclic aromatic ligands having up to25 rings and up to 100 carbon atoms and up to 10 hetero atoms selectedfrom nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, boron,antimony, tellurium, silicon, germanium, and tin, such as, for example,η⁵ -cyclopentadienyl, η⁶ -benzene, η⁶ -mesitylene, η⁶-hexamethylbenzene, η⁶ -fluorene, η⁶ -naphthalene, η⁶ -anthracene, η⁶-chrysene, η⁶ -pyrene, η⁷ -cycloheptatrienyl, η⁶ -triphenylmethane, η¹²-paracyclophane, η¹² -1,4-diphenylbutane, η⁵ -pyrrole, η⁵ -thiophene, η⁵-furan, η⁶ -pyridine, η⁶ -Y-picoline, η⁶ -quinaldine, η⁶ -benzopyran, η⁶-thiochrome, η⁶ -benzoxazine, η⁶ -indole, η⁶ -acridine, η⁶ -carbazole,η⁶ -triphenylene, η⁶ -silabenzene, η⁶ -arsabenzene, η⁶ -stibabenzene, η⁶-2,4,6-triphenylphosphabenzene, η⁵ -selenophene, η⁶ -dibenzostannepine,η⁵ -tellurophene, η⁶ -phenothiarsine, η⁶ -selenanthrene, η⁶-phenoxaphosphine, η⁶ -phenarsazine, η⁶ -phenatellurazine, and η⁶-1-phenylborabenzene. Other suitable aromatic compounds can be found byconsulting any of many chemical handbooks.

As mentioned before, the ligand can be a unit of a polymer, for examplethe phenyl group in polystyrene, poly(styrene-cobutadiene),poly(styrene-comethyl methacrylate), poly(α-methylstyrene),polyvinylcarbazole, and polymethylphenylsiloxane; the cyclopentadienegroup in poly(vinylcyclopentadiene), poly(η¹ -cyclopentadiene); thepyridine group in poly(vinylpyridine), etc. Polymers having a weightaverage molecular weight up to 1,000,000 or more can be used. It ispreferable that 5 to 50 percent of the unsaturated or aromatic groupspresent in the polymer be complexed with metallic cations.

Each of the ligands L^(1a), L^(1b), L^(1c), L^(1d), and L⁷ can besubstituted by groups that do not interfere with the complexing of theligand with the metal atom or which do not reduce the solubility of theligand to the extent that complexing with the metal atom does not takeplace. Examples of substituting groups, all of which preferably haveless than 30 carbon atoms and up to 10 hetero atoms selected fromnitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony,tellurium, silicon, germanium, tin, and boron, include hydrocarbylgroups such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl,benzyl, allyl, benzylidene, ethenyl, and ethynyl; hydrocarbyloxy groupssuch as methoxy, butoxy, and phenoxy; hydrocarbylmercapto groups such asmethylmercapto (thiomethoxy), phenylmercapto (thiophenoxy);hydrocarbyloxycarbonyl such as methoxycarbonyl and phenoxycarbonyl;hydrocarbylcarbonyl such as formyl, acetyl, and benzoyl;hydrocarbylcarbonyloxy such as acetoxy, benzoxy, andcyclohexanecarbonyloxy; hydrocarbylcarbonamido, e.g., acetamido,benzamido; azo; boryl; halo, e.g., chloro, iodo, bromo, and fluoro,hydroxy; cyano; nitro; nitroso, oxo; dimethylamino; diphenylphosphino,diphenylarsino; diphenylstibine; trimethylgermane; tributyltin;methylseleno; ethyltelluro; and trimethylsiloxy; condensed rings such asbenzo, cyclopenta; naphtho, indeno; and the like.

Ligands L^(2a), L^(2b), L^(2c), and L^(2d) in Formula I, and L⁸ inFormula II are provided by monodentate and polydentate compoundspreferably containing up to about 30 carbon atoms and up to 10 heteroatoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic,selenium, antimony, and tellurium, in addition to the metal atom,following loss of zero, one, or two hydrogens, the polydentate compoundspreferably forming with the metal, M^(a), M^(b), M^(c), M^(d), andM^(m), a 4-, 5-, or 6-membered saturated or unsaturated ring. Examplesof suitable monodentate compounds or groups are carbon monoxide, carbonsulfide, carbon selenide, carbon telluride, alcohols such as ethanol,butanol, and phenol; nitrosonium (i.e., NO⁺); compounds of Group VAelements such as ammonia, phosphine, trimethylamine, trimethylphosphine,triphenylamine, triphenylphosphine, triphenylarsine, triphenylstibine,tributylphosphite, isonitriles such as phenylisonitrile,butylisonitrile; carbene groups such as ethoxymethylcarbene,dithiomethoxycarbene; alkylidenes such as methylidene, ethylidene;suitable polydentate compounds or groups include1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylarsino)ethane,bis(diphenylphosphino)methane, ethylenediamine, propylenediamine,diethylenetriamine, 1,3-diisocyanatopropane, andhydridotripyrazolylborate; the hydroxycarboxylic acids such as glycollicacid, lactic acid, salicylic acid; polyhydric phenols such as catecholand 2,2'-dihydroxybiphenyl; hydroxyamines such as ethanolamine,propanolamine, and 2-aminophenol; dithiocarbamates such asdiethyldithiocarbamate, dibenzyldithiocarbamate; xanthates such as ethylxanthate, phenyl xanthate; the dithiolenes such asbis(perfluoromethyl)-1,2-dithiolene; aminocarboxylic acids such asalanine, glycine and o-aminobenzoic acid; dicarboxylic diamides such asoxalamide, biuret; diketones such as 2,4-pentanedione; hydroxyketonessuch as 2-hydroxyacetophenone; α-hydroxyoximes such as salicyladoxime;ketoximes such as benzil oxime; and glyoximes such as dimethylglyoxime.Other suitable groups are the inorganic groups such as, for example,CN⁻, SCN⁻, F⁻, OH⁻, Cl⁻, Br⁻, I⁻, and H⁻ and the organic groups such as,for example, acetoxy, formyloxy, benzoyloxy, etc. As mentioned before,the ligand can be a unit of a polymer, for example the amino group inpoly(ethyleneamine); the phosphino group inpoly(4-vinylphenyldiphenylphosphine); the carboxylic acid group inpoly(acrylic acid); and the isonitrile group inpoly(4-vinylphenylisonitrile).

Suitable radicals L^(3a), L^(3b), L^(3c), and L^(3d) in Formula Iinclude any group having in its structure an atom with an unsharedelectron. Suitable groups can contain any number of carbon atoms andhetero atoms but preferably contain less than 30 carbon atoms and up to10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus,arsenic, selenium, antimony, tellurium, silicon, germanium, tin, andboron. Examples of such groups are hydrocarbyl groups such as methyl,ethyl, propyl, hexyl, dodecyl, phenyl, tolyl, etc.; unsaturatedhydrocarbyl groups such as vinyl, allyl, butenyl, cyclohexenyl; thehydrocarbyl derivatives of a Group IVA element such astrimethylgermanium, triphenyltin, and trimethylsilyl, etc.; and organicgroups such as formyl, acetyl, propionyl, acryloyl, octadecoyl, benzoyl,toluenesulfonyl, oxalyl, malonyl, o-phthaloyl.

Ligand L⁴ in Formula I is provided by any monomeric or polymericcompound having an accessible unsaturated group, such as an acetylenic,--C.tbd.C-- group or an aromatic group which have accessible π-electronsregardless of the total molecular weight of the compound.

Illustrative of ligand L⁴ are the linear and cyclic diene and acetyleniccompounds preferably having less than 60 carbon atoms and up to 10hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus,arsenic, selenium, boron, antimony, tellurium, silicon, germanium, andtin, such as for example, acetylene, methylacetylene, diacetylene,butadiene, 1,2-dimethylacetylene, 1,3-cyclohexadiene, cyclopentadiene,and 1,4-cyclohexadiene; η³ -allyl, η³ -pentenyl, norbornadiene, η⁵-cyclohexadienyl, η⁶ -cycloheptatriene, η⁸ -cyclooctatetracene, andsubstituted and unsubstituted carbocyclic and heterocyclic aromaticligands having up to 25 rings and up to 100 carbon atoms and up to 10hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus,arsenic, selenium, boron, antimony, tellurium, silicon, germanium, andtin, such as, for example, η⁵ -cyclopentadienyl, η⁶ -benzene, η⁶-mesitylene, η⁶ -hexamethylbenzene, η⁶ -fluorene, η⁶ -naphthalene, η⁶-anthracene, η⁶ -chrysene, η⁶ -pyrene, η⁷ -cycloheptatrienyl, η⁶-triphenylmethane, η⁵ -pyrrole, η⁵ -thiophene, η⁵ -furan, η⁶ -pyridine,η⁶ -Y-picoline, η⁶ -quinaldine, η⁶ benzopyran, η⁶ -thiochrome, η⁶-benzoxazine, η⁶ -indole, η⁶ -acridine, η⁶ -carbazole, η⁶-(1,2,3,4,4a,12a)-η⁶ -(7,8,9,10,10a,10b)chrysene, η⁶ -triphenylene,η⁶,η^(6') -paracyclophane, η⁶,η^(6') -1,4-diphenylbutane, η⁶-silabenzene, η⁶ -arsabenzene, η⁶ -stibabenzene, η⁶-2,4,6-triphenylphosphabenzene, η⁵ -selenophene, η⁶ -dibenzostannepine,η⁵ -tellurophene, η⁶ -phenothiarsine, η⁶ -selenanthrene, η⁶-phenoxaphosphine, η⁶ -phenarsazine, η⁶ -phenatellurazine, and η⁶-1-phenylborabenzene. Other suitable aromatic compounds can be found byconsulting any of many chemical handbooks.

Each of the ligands L⁴ can be substituted by groups that do notinterfere with the complexing of the ligand with the metal atom or whichdo not reduce the solubility of the ligand to the extent that complexingwith the metal atom does not take place. Examples of substitutinggroups, all of which preferably have less than 30 carbon atoms and up to10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus,arsenic, selenium, antimony, tellurium, silicon, germanium, tin, andboron, include hydrocarbyl groups such as methyl, ethyl, butyl, dodecyl,tetracosanyl, phenyl, benzyl, allyl, benzylidene, ethenyl, and ethynyl;hydrocarbyloxy groups such as methoxy, butoxy, and phenoxy;hydrocarbylmercapto groups such as methylmercapto (thiomethoxy),phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such asmethoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl,acetyl, and benzoyl; hydrocarbylcarbonyloxy such as acetoxy, benzoxy,and cyclohexanecarbonyloxy; hydrocarbylcarbonamido, e.g., acetamido,benzamido; azo; boryl; halo, e.g., chloro, iodo, bromo, and fluoro,hydroxy; cyano; nitro; nitroso, oxo; dimethylamino; diphenylphosphino,diphenylarsino; diphenylstibine; trimethylgermane; tributyltin;methylseleno; ethyltelluro; and trimethylsiloxy; condensed rings such asbenzo, cyclopenta; naphtho, indeno; and the like.

Ligand L⁵ is provided by monodentate and polydentate compoundspreferably containing up to about 30 carbon atoms and up to 10 heteroatoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic,selenium, antimony, and tellurium. Examples of suitable monodentatecompounds or groups are carbon monoxide, carbon sulfide, carbonselenide, carbon telluride, alcohols such as ethanol, butanol, andphenol; nitrosonium (i.e., NO⁺); compounds of Group VA elements such astriphenylamine, triphenylphosphine, triphenylarsine, triphenylstibine,isonitriles such as phenylisonitrile; suitable polydentate compounds orgroups include 1,2-bis(diphenylphosphino)ethane,1,2-bis(diphenylarsino)ethane, bis(diphenylphosphino)methane,ethylenediamine, propylenediamine, diethylenetriamine,1,3-diisocyanatopropane, and hydridotripyrazolylborate; thehydroxycarboxylic acids such as glycollic acid, lactic acid, salicylicacid; polyhydric phenols such as catechol and 2,2'-dihydroxybiphenyl;hydroxyamines such as ethanolamine, propanolamine, and 2-aminophenol;dithiocarbamates such as diethyldithiocarbamate,dibenzyldithiocarbamate; xanthates such as ethyl xanthate, phenylxanthate; the dithiolenes such as bis(perfluoromethyl)-1,2-dithiolene;aminocarboxylic acids such as alanine, glycine and o-aminobenzoic acid;dicarboxylic diamides such as oxalamide, biuret; diketones such as2,4-pentanedione; hydroxyketones such as 2-hydroxyacetophenone;α-hydroxyoximes such as salicyladoxime; ketoximes such as benzil oxime;and glyoximes such as dimethylglyoxime. Other suitable groups are theinorganic groups such as, for example, CN⁻, SCN⁻, F⁻, OH⁻, Cl⁻. Br⁻, I⁻,and H⁻ and the organic groups such as, for example, acetoxy, formyloxy,benzoyloxy, etc.

Suitable radical L⁶ in Formula I includes any group having in itsstructure an atom with two or more unpaired electrons. Suitable groupscan contain any number of carbon atoms and hetero atoms but preferablycontain less than 30 carbon atoms and up to 10 hetero atoms selectedfrom nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony,tellurium, silicon, germanium, tin, and boron. Examples of such groupsare hydrocarbyl groups such as methenyl, ethenyl, propenyl, hexenyl,dodecenyl, methinyl, and carbide.

Suitable anions, X, in Formulas I and II, of use as the counterion inthe ionic salts of the organometallic complex cation in the preferredradiation-sensitive compositions of the invention are those in which Xhas the formula DQ_(r), wherein D is a metal from Groups IB to VIIIB ora metal or metalloid from Groups IIIA to VA of the Periodic Chart ofElements, Q is a halogen atom, and r is an integer having a value of 1to 6. Preferably, the metals are copper, zinc, titanium, vanadium,chromium, manganese, iron, cobalt, or nickel and the metalloidspreferably are boron, aluminum, antimony, tin, arsenic, and phosphorus.Preferably, the halogen, Q, of Formula II, is chlorine or fluorine.Illustrative of suitable anions are BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, FeC₁₄⁻, SnCl⁵ ⁻, SbFl₅.sup.═, AlFl₆.sup..tbd., GaCl₄ ⁻, InF₄ ⁻, TiF₆.sup.═,ZrF₆ ⁻, etc. Preferably, the anions are BF₄ ⁻ , PF₆ ⁻, SbF₆ ⁻, SbF₅ OH⁻,AsF₆ ⁻, and SbCl₆ ⁻. Most preferably, the anions are AsF₆ ⁻, SbF₆ ⁻, andSbF₅ OH⁻. Some of the organometallic complex salts having these threeanions are novel and all of these salts provide compositions of theinvention that are relatively more active toward polymerization onexposure to energy than are salts having other anions.

Ligand L⁹ in Formula III is provided by linear and cyclic olefiniccompounds formally described as having lost a hydride or a proton alphato a double bond from a saturated carbon and having less than 10 carbonatoms and no heteroatoms, such as for example η³ -allyl, η³ -butenyl, η³-pentenyl, η³ -hexenyl, η³ -heptenyl, η³ -octenyl, η³ -nonenyl, η³-decenyl, η³ -cyclobutenyl, η³ -cyclopentenyl, η³ -cyclohexenyl, η³-cycloheptenyl, η³ -cyclooctenyl, η³ -cyclononenyl, η³ -cyclodecenyl, η⁵-methylcyclopentadienyl, η⁵ -cyclopentadienyl, η⁵-pentamethylcyclopentadienyl, η⁵ -cyclohexadienyl, and η⁷-cycloheptatrienyl (it being understood that both the η⁵-cyclopentadienyl and the η⁷ -cycloheptatrienyl ligand may be formallydescribed as an aromatic ligand) and aromatic ligands having up to 4rings and up to 24 carbon atoms and up to 2 heteroatoms selected fromnitrogen, oxygen, and sulfur, such as, for example, η⁶ -toluene, η⁶-ethylbenzene, η⁶ -isopropylbenzene, η⁶ -propylbenzene, η⁶-t-butylbenzene, η⁶ -m-xylene, η⁶ -o-xylene, η⁶ -p-xylene, η⁶-1,3,5-trimethylbenzene (mesitylene), η⁶ -1,2,4-trimethylbenzene, η⁶-1,3,5-triisopylbenzene, η⁶ -1,2,3,4-tetramethylbenzene, η⁶-1,2,3,5-tetramethylbenzene, η⁶ -1,2,4,5-tetramethylbenzene (durene), η⁶-pentamethylbenzene, η⁶ -hexamethylbenzene, η⁶ -phenol, η⁶ -thiophenol,η⁶ -anisole, η⁶ -thioanisole, η⁶ -aniline, η⁶ -N,N-dimethylaniline, η⁶-diphenyl amine, η⁶ -diphenylmethane, η⁶ -triphenylmethane, η⁶-chlorobenzene, η⁶ -bromobenzene, η⁶ -fluorobenzene, η⁶ -cyanobenzene,η⁶ -nitrobenzene, η⁶ -fluorene, η⁶ -carbazole, η⁶ -biphenyl, η⁶-triphenylene, η⁶ -naphthalene, η⁶ -anthracene, η⁶ -phenanthracene, η⁶-pyrene, η⁶ -chrysene, η⁶ -tetralin, η⁶ -ethoxybenzene, η⁶ -benzoicacid, η⁶ -quinoline, η⁶ -isoquinoline, η⁶ -indole, η⁶ -benzimidazole, η⁶-1,2-benzopyrazole, η⁶ -benzothiazole, η⁶ -benzoxazole, η⁶ -indan, η⁶-paracyclophane, η⁶ -1,4-diphenylbutane, η¹² -paracyclophane, η¹²-1,4-diphenylbutane, poly(η⁶ -styrene), poly(η⁶ -N-vinylcarbazole),poly(η⁶ -methylphenylsiloxane), (η⁶-1,2,3,4,4a,9a)-9-(phenylmethylidene)fluorene, and (η⁶-1,2,3,4,4a,9a)-9-(3-phenyl-2-propenylidene)fluorene. The latter twoligands may be mono-substituted by groups selected from methyl, ethyl,propyl, isopropyl, methoxy, ethoxy, hydroxy, nitro, chloro, bromo,amino, and N,N-dimethylamino on the phenyl ring. Also, the latter twoligands may be disubstituted by groups that may be same or differentselected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy,hydroxy, nitro, chloro, bromo, amino, and N,N-dimethylamino on thephenyl ring in the 2,3; 2,4; or 3,4 positions.

There are restrictions on the total sum of electrons donated by theligands, L^(1a), L^(2a), L^(3a), L^(1b), L^(2b), L^(3b), L^(1c), L^(2c),L^(3c), L^(1d), L^(2d), L^(3d), L⁴, L⁵ and L⁶ of Formula I, L⁷ and L⁸ ofFormula II, and L⁹ and L¹⁰ of Formula III and the valence electronspossessed by the metal, M^(a), M^(b), M^(c), M^(d), M^(m), and M^(p).For most complex compounds not involving intramolecular metal-metalbonding, this sum is governed by the "eighteen electron rule" [see J.Chem. Ed., 46, 811 (1969)]. This rule is sometimes called the "nineorbital rule", "the effective number rule", or the "rare gas rule". Thisrule states that the most stable organometallic compounds tend to bethose compounds in which the sum of the electrons donated by the ligandsand the metal is eighteen. Those skilled in the art, however, know thatthere are exceptions to this rule and that organometallic complexcompounds having a sum of 16, 17, 19, and 20 electrons are also known.Therefore, ionic salts of organometallic complex cations not includingintramolecular metal-metal bonding are described by Formulas I, II, andIII in which complexed metal M^(a), M^(b), M^(c), M^(d), M^(m) and M^(p)have a total sum of 16, 17, 18, 19, or 20 electrons in the valence shelland a residual net positive charge of 1, 2 or 3 are included within thescope of the invention.

For complex compounds described in Formula I in which intramolecularmetal-metal bonding exists serious departure from the "eighteen electronrule" can occur. It has been proposed [J. Amer. Chem. Soc. 100, 5305(1978)] the departure from the "eighteen electron rule" in thesetransition metal complexes is due to the metal-metal interactionsdestabilizing the metal p orbitals to an extent to cause them to beunavailable for ligand bonding. Hence, rather than count electronsaround each metal separately in a metal cluster, cluster valenceelectrons (CVE) are counted. A dinuclear complex, M^(a) M^(b), is seento have 34 CVEs, a trinuclear complex, M^(a) M^(b) M^(c), 48 CVEs, and atetranuclear complex, M^(a) M^(b) M^(c) M^(d), having tetrahedron,butterfly, and square planar geometry is seen to have 60, 62, or 64CVEs, respectively. Those skilled in the art, however, know that thereare exceptions to this electron counting method and that organometalliccomplex cluster compounds having a sum of 42, 44, 46, 50 CVEs for atrinuclear complex and 58 CVEs for a tetranuclear complex are alsoknown. Therefore, ionic salts of di, tri, or tetranuclear organometalliccomplex cations are described by Formula I in which the complexed metalcluster, M^(a) M^(b), M^(a) M^(b) M^(c), or M^(a) M^(b) M^(c) M^(d) hasa total sum of 34; 42, 44, 46, 48, 50; or 58, 60, 62, 64 CVEs in thevalence shell, respectively, and a residual net positive charge of 1, 2,or 3 are included within the scope of this invention.

Suitable organometallic complex ionic salts described by Formulas I, II,III of use in the compositions of the invention are those salts thatupon application of sufficient energy, either thermal or electromagneticradiation having a wavelength from about 200 to 600 nm, will generate anactive species capable of initiating cationic polymerization. The levelof cationic activity will, of course, depend on the choice of metal,ligands, and counterions in the salt.

Suitable ionic salts that are activated by heat to initiate cationicpolymerization are those that will add an intermediate strengthnucleophile such as substituted or unsubstituted trialkyl- andtriarylphosphines (preferably triphenylphosphine), trialkyl- andtriarylphosphites, pyridines, and anilines. Examples of such compoundsare described in Tetrahedron, 34, 3047 (1978) and "Carbonium Ions", 5,Chapter 37, 1976, Wiley-Interscience, New York. These reviews containreferences to the experimental procedures used to determine if aparticular compound will add such a nucleophile.

Suitable ionic salts that are activated by electromagnetic radiation toinitiate cationic polymerization are those that upon photolysis liberateat least one coordination site on the metal. The ability to liberate atleast one coordination site upon photolysis can be verified by doing aligand exchange experiment. In such an experiment, the compound

    [(L.sup.1a)(L.sup.2a)(L.sup.3a)M.sup.a ].sub.g [(L.sup.1b)(L.sup.2b)(L.sup.3b)M.sup.b ].sub.h [(L.sup.1c)(L.sup.2c)(L.sup.3c)M.sup.c ].sub.j[(L.sup.ad)(L.sup.2d)(L.sup.3d)M.sup.d ].sub.k (L.sup.4)(L.sup.5)(L.sup.6).sup.+e X.sub.f                I

is photolyzed in the presence of a potential entering ligand L (L can beof the L¹ or L² types). That L has indeed added or exchanged with atleast one ligand L¹ to L⁶ of Formula I can be determined by any numberof analytical techniques. It is particularly convenient for thisdetermination to use some spectroscopic technique to monitor thereaction before, during, and after photolysis. If L or at least one ofthe L^(2a), L^(2b), L^(2c), L^(2d), or L⁵ ligands is carbon monoxide,then infrared spectroscopy is a well suited technique to monitor thereaction. Otherwise UV/visible or NMR spectroscopy can be employed. Thespectrum before photolysis can be compared with that taken aftercompletion of the reaction to determine if the suspected ligandsubstituted product is present. A more rigorous method would involveisolation of the photoproduct after completion of the reaction and useof an analytical technique such as elemental analysis to verify that Lhas indeed entered the coordination sphere of the metal. The properconditions under which the ligand exchange experiment should be carriedout, i.e. organometallic ionic salt concentration, identity of theentering ligand, entering ligand concentration, choice of solvent,irradiation wavelength, irradiation time, light source, light sourceintensity, reaction vessel, presence or absence of oxygen, analysistechnique, etc. must be adjusted by the experimentalist for theparticular system under study. Examples of the conditions which havebeen used to study ligand exchange reactions are contained in"Organometallic Photochemistry", 1979, Academic Press, New York, andreferences therein, and in Inorg. Chem., 19, 3007 (1980).

Examples of suitable salts of organometallic complex cations useful inthe composition of the invention include the following (proposedstructures of typical compounds are shown at the end of the list):

(η⁵ -cyclopentadienyl)tricarbonyliron(1+) hexafluorophosphate.sup.(a)

(η⁵ -cyclopentadienyl)dicarbonylthiocarbonyliron(1+) tetrafluoroborate

(η⁵ -cyclopentadienyl)carbonylbis(triphenylstibine)iron(1+)hexafluorophosphate

(η⁵ -cyclopentadienyl)tricarbonylruthenium(1+) tetrachloroferrate

(η⁵ -cyclopentadienyl)dicarbonyltriphenylstibineiron(1+)hexafluoroantimonate

(η⁵ -methylcyclopentadienyl)dicarbonylnitrosylmanganese(1+)hexafluoroantimonate.sup.(b)

(η⁵ -methylcyclopentadienyl)(η³ -allyl)dicarbonylmanganese(1+)tetrafluoroborate.sup.(c)

(η⁵ -cyclopentadienyl)tetracarbonylmolybdenum(1+) hexafluorophosphate

(η⁵ -pentadienyl)tricarbonyliron(1+) tetrafluoroborate

(η⁵ -cyclohexadienyl)tricarbonyliron(1+) hexafluoroarsenate.sup.(d)

(η⁵ -cyclohexadienyl)(ethylidene)carbonyltriphenylphosphineiron(1+)tetrafluoroborate

(η⁵-cyclopentadienyl)(ethoxymethylcarbene)carbonyltriphenylphosphineiron(1+)tetrafluoroborate

(η⁵ -cyclopentadienyl)(dithiomethoxycarbene)dicarbonyliron(1+)hexafluorophosphate

(η⁵ -cyclopentadienyl)dicarbonylmethylisonitrileiron(1+)hexafluoroarsenate

bis(η⁵ -cyclopentadienyl)(η² -ethylene)(o-methyl)tungsten(1+)hexafluorophosphate

(η⁶ -toluene)tricarbonylmanganese(1+) hexafluoroantimonate.sup.(e)

(η⁶ -mesitylene)tricarbonylrhenium(1+) hexafluoroantimonate

(η⁷ -cycloheptatrienyl)tricarbonylchromium(1+) hexafluorophosphate

(η⁷ -cycloheptatrienyl)tricarbonyltungsten(1+)hexafluoroarsenate.sup.(f)

(η⁵ -cyclopentadienyl)(η² -1-pentene)dicarbonyliron(1+)tetrafluoroborate

(η⁶ -benzene)(η⁵ -cyclopentadienyl)iron(1+) hexafluorophosphate

(η⁶ -mesitylene)(η⁵ -cyclopentadienyl)iron(1+) tetrafluoroborate

(η⁶ -naphthalene)(η⁵ -cyclopentadienyl)iron(1+) hexafluoroantimonate

(η⁶ -acetophenone)(η⁵ -methylcyclopentadienyl)iron(1+)hexafluoroarsenate

bis(η⁵ -cyclopentadienyl)cobalt(1+) hexafluorophosphate

bis(η⁵ -cyclopentadienyl)iron(1+) hexafluoroantimonate

bis(η⁵ -chlorocyclopentadienyl)nickel(1+) hexafluorophosphate

bis(η⁶ -benzene)chromium(1+) hexafluoroantimonate.sup.(g)

bis(η⁶ -hexamethylbenzene)cobalt(2+) hexafluoroarsenate

bis(η⁶ -hexamethylbenzene)nickel(2+) hexafluoroantimonate

tetracarbonyltriphenylphosphinecobalt(1+) hexafluorophosphate

tricarbonylbis(triphenylphosphine)iridium(1+) hexafluorophosphate

(η³ -allyl)pentacarbonylchromium(1+) tetrafluoroborate

pentacarbonylnitrosylmolybdenum(1+) hexafluorophosphate

(η³ -allyl)tetracarbonyliron(1+) hexafluoroantimonate

hexacarbonylrhenium(1+) hexafluoroantimonate

bis(η⁶ -mesitylene)iron(2+) hexafluoroantimonate.sup.(h)

bis(η⁶ -hexamethylbenzene)manganese(1+) tetrafluoroborate

bis(η⁶ -mesitylene)vanadium(1+) hexafluorophosphate

(η⁷ -cycloheptatrienyl)(η⁵ -cyclopentadienyl)manganese(1+)hexafluoroarsenate

(η⁸ -cyclooctatetrenyl)(η⁵ -cycIopentadienyl)chromium(1+)hexafluorophosphate

(η⁵ -fluorene)(η⁵ -cyclopentadienyl)iron(1+) hexafluorophosphate.sup.(i)

(η⁶ -1-phenylborabenzene)(η⁵ -cyclopentadienyl)cobalt(1+)hexafluorophosphate

(η⁵ -cyclopentadienyl)(η⁵ -N-methylpyrrolyl)iron(1+) hexafluorophosphate

(η⁶ -2,3,4,5-tetrathiomethoxybenzene)(η⁵ -cyclopentadienyl)iron(1+)hexafluoroarsenate

[(η⁶ -1,2,3,4,5,6)(η⁶ -7,8,9,10,11,12)biphenyl]bis(η⁵-cyclopentadienyl)diiron(2+) tetrafluoroborate

[(η⁶ -1,2,3,4,4a,9a)(η⁶ -5,6,7,8,8a,5a)fluorene]bis(η⁵-cyclopentadienyl)diiron(2+) hexafluorophosphate

[(η⁶ -1,2,3 4 4a 9a)(η⁶ -5,6,7,8,8a,5a)fluorene]bisenzene)diiron(4+)hexafluorophosphate

[(η⁶ -1,2,3,4,4a,12a)(η⁶ -7,8,9,10,10a,6a)chrysene]bis(η⁶-benzene)dichromium(2+) hexafluoroantimonate

dicarbonyl[bis(diphenylphosphino)ethane]bis(η⁵-cyclopentadienyl)diiron(1+) hexafluorophosphate

tetra[(η⁵ -cyclopentadienyl)carbonyliron](1+) hexafluorophosphate

tris[(η⁶ -benzene)cobalt]dicarbonyl(1+) hexafluorophosphate

tris(η⁵ -cyclopentadienyl)dinickel(1+) hexafluorophosphate

[(η⁶ -1,2,29,18c,18b,18a)(η⁶ -7,8,8a,18i,18h,7a)(η⁶-13,14,14a,18o,18n,12a)(η⁶-18t,18u,18v,18w,13x,18y)-tripyreno(2,1,10,9,8,7-defghij:2',1',10',9',8',7'-nopqrst:2",1",10",9",8",7"-xyza,b,c,d(trinaphthalene]tetra(η⁵-cyclopentadienyl)tetrairon(4+) hexafluoroantimonte

[(η⁶ -4,5,5a,28b,3a)(η⁶ -8a,8b,20d,22a,22b,24c)-1H,14H dipyrano(3,4,6,gh: 3',4',5'-g'h'anthra(2",1",9":4,5,6;6",5",10":4',5',6')diisoquino(2,1-a:2',1'-a¹)diperimidine]bis(.eta.⁵-cyclopentadienyl)diiron(2+) hexafluoroantimonate

[(η⁶ -1,2,3,3a,13b,13a)benzo(10,11)chryseno(2,3-d)(1,3)dioxole](η⁵-methylcyclopentadienyl)iron(1+) hexafluorophosphate

[(η⁶ -1,2,3,3a,16c,16b)(η⁶-9,10,11,11a,13c,8b)cycloocta(1,2,3,4-def:5,6,7,8-d'e'f')diphenanthrene]bis(η⁵-acetylcyclopentadienyl)diiron(2+) tetrafluoroborate

bis(η⁵ -acetylcyclopentadienyl)iron(1+) tetrafluoroborate

[(η⁶ -1,2,3,4,4a,42a)(η⁶ -16,17,18,19,19a,15a)(η⁶ -30,31,32,32a,32b,29a)naphth(8',1',2':6,5,10)anthra(2,3-i)naphth(2''',3''':6'',7'')indolo(2",3":5"6")naphth(2'3':4,5)indolo(2,3-g)naphtho(2,3-i')benzo(1,2-a:4,5-a')dicarbazole]tris(⁵-cyclopentadienyl)triiron(3+) hexafluoroantimonate

(η³ -1-methyl-allyl)tricarbonyliron(+1) hexafluorophosphate

(η³ -1,3-dimethyl-allyl)tricarbonyliron(+1) hexachloroantimonate

[(η⁵ -cyclopentadienyl)nickelnonacarbonyltricobalt](+1)hexafluorophosphate

Di-(μ-carbonyltricarbonyl)(dicarbonyliron)(hexacarbonyl-μ-hydrodiruthenium)-82-hydro-osmium(2Fe-Ru)(Fe-Os)(2Os-Ru)(Ru-Ru)(+1)hexafluorophosphate.sup.(j)

Tetra-μ-hydrotetrakis[(1,2,3,4,5-η)-1,2,3,4,5-pentamethyl-2,4-cyclopentadienyl-1-yl]-tetra-tetrahedro-rhodium(+2)bis(hexafluorophosphate).sup.(k)

Bis(μ-diphenylphosphido-μ-carbonyl-μ-methylcyclopentadienylcarbonyliron)rhodium(2Rh-Fe)(+1)hexafluorophosphate.sup.( 1)

Di-μ-carbonylpentacarbonyl-μ-carbonyldi-π-cyclopentadienyldirhodio)diiron(Fe-Fe)(4Fe-Rh)(Rh-Rh)(+1)hexafluoroarsenate(m)

Di-μ3-carbonyltricarbonylbis(π-cyclopentadienylnickelio)iron(2Fe-Ni)(Ni-Ni)(+1)hexafluoroantimonate.sup.(n) ##STR2##

Cationically polymerizable materials that can be cured or polymerized bythe compounds of this invention, using the latter in a catalyticallyeffective amount, are those known to undergo cationic polymerization andinclude 1,2-, 1,3-, and 1,4-cyclic ethers (also designated as 1,2-,1,3-, and 1,4-epoxides), vinyl ethers, N-vinyl compounds, ethylenicallyunsaturated hydrocarbons, cyclic formals, and cyclic organosiloxanes, Anextensive list of cationically polymerizable monomers which can be usedin this invention are given in U.S. Pat. Nos. 3,347,676 and 3,842,019.

The cyclic ethers which can be polymerized in accordance with thisinvention include those described in "Ring-Opening Polymerizations",Vol. 2, by Frisch and Reegan, Marcel Dekker, Inc. (1969). Suitable1,2-cyclic ethers are the monomeric and polymeric types of epoxides.They can be aliphatic cycloaliphatic, aromatic, or heterocyclic and willtypically have an epoxy equivalency of from 1 to 6, preferably 1 to 3.Particularly useful are the aliphatic, cycloaliphatic, and glycidylether type 1,2-epoxides such as propylene oxide, epichlorohydrin,styrene oxide, vinylcyclohexene oxide, vinylcyclohexene dioxide,glycidol, butadiene oxide, glycidyl methacrylate, diglycidyl ether ofbisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadienedioxide, epoxidized polybutadiene, 1,4-butanediol ether, polyglycidylether of phenolformaldehyde resole or novolak resin, resorcinoldiglycidyl ether, and epoxy silicones, e.g., dimethylsiloxanes havingcycloaliphatic epoxide or glycidyl ether groups. A wide variety ofcommercial epoxy resins are available and listed in "Handbook of EpoxyResins" by Lee and Neville, McGraw Hill Book Company, New York (1967)and in "Epoxy Resin Technology" by P. F. Bruins, John Wiley & Sons, NewYork (1968). Representative of the 1,3- and 1,4-cyclic ethers which canbe polymerized in accordance with this invention are oxetane,3,3-bis(chloromethyl)oxetane, and tetrahydrofuran.

Another useful class of cationically-sensitive monomers which can bepolymerized in accordance with the invention is represented by thegeneral formula:

    CH.sub.2 ═C(Y)NR',

where X is --O-- or --NR"---- (where R" is hydrogen or lower alkyl), R'is hydrocarbyl, hydrocarbylcarbonyl, halohydrocarbyl, orhydroxyhydrocarbyl when X is oxygen, or R' is hydrocarbyl,hydrocarbylcarbonyl, or hydrocarbylsulfonyl when X is nitrogen, and Y ishydrogen, alkyl, aryl, or other hydrocarbyl, or R' (ashydrocarbylcarbonyl) and R" can be connected to form a 5- or 6-memberedcyclic structure containing nitrogen as a hetero ring atom. The term"hydrocarbyl" is used herein in its usual sense to mean alkyl, alkenyl,aryl, cycloalkyl, cycloalkenyl, alkaryl, arylalkyl, and the like. Ingeneral, monomers of this type contain a vinyl group and are typified byvinyl alkyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyln-butyl ether, vinyl 2-chloroethyl ether, vinyl isobutyl ether, vinylphenyl ether and vinyl 2-ethylhexyl ether, vinyl ethers of substitutedaliphatic alcohols such as 1,4-di(ethenoxy)butane, vinyl 4-hydroxybutylether, and N-vinyl compounds such as N-vinyl-N-methyl octanesulfonamideand N-vinylpyrrolidone. A description of vinyl monomers and their use inpreparing polymers is set forth in "Vinyl and Related Polymers," bySchildknecht, published by John Wiley & Sons, Inc., New York (1952).

Other cationically-sensitive monomers which can be polymerized in thisinvention include ethylenically unsaturated hydrocarbons such asisobutylene, 1,3-butadiene, isoprene, styrene, and divinylbenzene;cyclic formals such as trioxane, 1,3-dioxolane, 2-vinyl-1,3-dioxolaneand 2-methyl-1,3-dioxolane; and cyclic siloxanes which can containvarious groups attached to the silicon atom such as a hydrocarbonradical (alkyl, aryl, alkaryl), an alkenyl hydrocarbon radical (vinyl,allyl or acryloyloxy-alkyl), a halogenated hydrocarbon radical, acarboxy-containing hydrocarbon radical or ester group, acyanohydrocarbon radical, hydrogen, halogen or a hydroxy group.Representative cyclic siloxanes are hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane,vinylheptamethylcyclotetrasiloxane,methacryloyloxymethylheptamethylcyclotetrasiloxane,2-bromoethylheptamethylcyclotetrasiloxane,3-chloropropylheptamethylcyclotetrasiloxane,1,2,3-tri(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane,acetoxymethylheptamethylcyclotetrasiloxane,cyanomethylheptamethylcyclotetrasiloxane,1,2,3-trihydrotrimethylcyclotrisiloxane, andchloroheptamethylcyclotetrasiloxane. Other known cyclic siloxanes arelisted in "Chemistry and Technology of Silicones" by Walter Noll,Academic Press, New York (1968), Tables 41, 44 and 45.

The cyclic siloxanes can also be polymerized in the presence ofrelatively low molecular weight linear siloxanes such ashexamethyldisiloxane, chloropentamethyldisiloxane andoctamethyltrisiloxane which serve to terminate the growing chain andprovide stable fluids or fluids having reactive end groups.

There is a host of commercially available cationically-sensitivemonomers which can be used in this invention. In particular, cyclicethers which are readily available include propylene oxide, oxetane,epichlorohydrin, tetrahydrofuran, styrene oxide, vinylcyclohexene oxide,glycidol, glycidyl methacrylate, octylene oxide, phenyl glycidyl ether,1,2-butane oxide, diglycidyl ether of bisphenol A (e.g., "Epon 828" and"DER 331"), vinylcyclohexene dioxide (e.g., "ERL-4206),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g.,"ERL-4221"), 3,4-epoxy-6-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexanecarboxylate (e.g., "ERL-4201"),bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (e.g., "ERL-4289"),aliphatic epoxy modified with polypropylene glycol (e.g., "ERL-4050" and"ERL-4052"), dipentene dioxide (e.g., "ERL-4269"), epoxidizedpolybutadiene (e.g., "Oxiron 2001"), silicone epoxy (e.g., "Syl-Kem90"), 1,4-butanediol diglycidyl ether (e.g., Araldite RD-2),polyglycidyl ether of phenolformaldehyde novolak (e.g., "DER-431","Epi-Rez 521" and "DER-438"), resorcinol diglycidyl ether (e.g.,"Kopoxite"), polyglycol diepoxide (e.g., "DER 736"), polyacrylateepoxide (e.g., "Epocryl U-14"), urethane modified epoxide (e.g.,"QX3599"), polyfunctional flexible epoxides (e.g., "Flexibilizer 151"),and mixtures thereof as well as mixtures thereof with co-curatives,curing agents, or hardeners which also are well known (see Lee andNeville and Bruins, supra). Representative of the co-curatives ofhardeners which can be used are acid anhydrides such as nadic methylanhydride, cyclopentanetetracarboxylic dianhydride, pyromelliticanhydride, cis-1,2-cyclohexanedicarboxylic anhydride, and mixturesthereof.

In general, the polymerization of cationically-sensitive monomers withthe ionic salt of an organometallic complex can be carried out at roomtemperature for the majority of cationically-sensitive monomers,although low temperature (e.g., -10° C.) or elevated temperatures (e.g.,30° to 200° C., preferably 50° to 150° C.), can be used to either subduethe exotherm of polymerization or to accelerate the polymerization. Inthe case of latent salt catalysts of this invention, temperaturesgenerally in the range of 50° to 250° C., preferably from 50° to 150°C., can be used. The temperature of polymerization and amount ofcatalyst will vary and be dependent on the particularcationically-sensitive monomer used and the desired application of thepolymerized or cured product. The amount of ionic salt of anorganometallic complex to be used as a catalyst in this invention shouldbe sufficient to effect polymerization of the cationically-sensitivemonomer (i.e., a catalytically effective amount) under the desired useconditions. Such amount generally will be in the range of about 0.01 to20 weight percent, preferably 0.5 to 5.0 weight percent, and mostpreferably 1.0 to 2.0 weight percent, based on the weight ofcationicallysensitive monomer.

Solvents can be used to assist in dissolution of the ionic salt in thecationically-sensitive material and are preferred for use in thepolymerizable compositions. Representative solvents include acetone,methyl ethyl ketone, cyclopentanone, methyl cellosolve acetate,methylene chloride, nitromethane, methylformate, acetonitrile, and1,2-dimethoxyethane (glyme).

The curable or polymerizable compositions of this invention comprisingthe cationically-sensitive monomer(s) and the ionic salt of anorganometallic complex as catalyst can be used for applications such asthose in which other cationically-sensitive compositions employing Lewisacid catalysts such as BF₃ or BF₃ ·diethyl ether or the radiationsensitive onium salts are used. Thus, the compositions can be used asadhesives, caulking and sealing compounds, casting and moldingcompounds, potting and encapsulating compounds, impregnating and coatingcompounds, etc. depending on the particular cationically-sensitivemonomer and ionic organometallic complex used. In addition, thecomposition may contain adjuvants (e.g., fillers, such as silica, talc,glass bubbles, clay, reinforcing fibers, dyes, pigments, plasticizers,slip agents, antioxidants, surface modifying agents, etc.,) as long asthey do not interfere with the polymerization of thecationically-sensitive components of the composition or, where the ionicsalt of the organometallic complex is radiation-sensitive, absorbradiation to which the complex is responsive.

For those compositions of the invention which are radiation-sensitive,i.e., the compositions containing cationically-sensitive monomers and anionic salt of an organometallic complex of Formulas I, II, and III, anysource of radiation emitting active radiation in the ultraviolet andvisible region of the spectrum (e.g., about 200 to 600 nm) can be used.Suitable sources of radiation include mercury vapor discharge lamps,carbon arcs, tungsten lamps, xenon lamps, sunlight, etc. The requiredamount of exposure to effect polymerization is dependent upon suchfactors as the identity and concentration of the organometallic ioniccomplex, the particular cationically-sensitive monomer, the thickness ofthe exposed material, type of substrate, intensity of the radiationsource and amount of heat associated with the radiation. Optionally, itis within the scope of this invention to include spectral sensitizers inthe radiation-sensitive composition. Any photosensitizer may be usefulif its triplet energy is at least 45 kcal/mole. Examples of suchsensitizers are given in Table 2-1 of the reference, Steven L. Murov,Handbook of Photochemistry, Marcel Dekker Inc., NY, 27-35 (1973), andinclude pyrene, fluoroanthrene, benzil, chrysene, p-terphenyl,acenaphthene, naphthalene, phenanthrene, and biphenyl. When present, theamount of sensitizer used in the practice of the present invention isgenerally in the range of 0.01 to 10 parts, and preferably 0.1 to 1.0parts, by weight of sensitizer per part of organometallic salt.

The objects and advantages of this invention are further illustrated bythe following examples, many of which utilize as cationically-sensitivemonomer a stock solution consisting of 1 part by weight ofvinylcyclohexene dioxide and 1 part by weight of3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboylate. The particularmaterials and amounts thereof recited in these examples, which are inparts by weight, as well as other conditions and details should not beconstrued to unduly limit this invention.

EXAMPLES 1-4

Polymerizable solutions were prepared by mixing in four suitable vessels10 parts of stock solution, 1.0 part of acetonitrile, and 0.1 part ineach vessel respectively, of (Example 1) the hexafluoroantimonate,(Example 2) the hexafluoroarsenate, (Example 3) the hexafluorophosphate,and (Example 4) the tetrafluoroborate salt of (η⁶ -mesitylene)(η⁵-cyclopentadienyl)iron(1+) (each prepared as described in W. A.Hendrickson, Ph.D. thesis, U. of Florida (1978)). The solutions werecoated onto polyvinylidene chloride primed 75 micrometer polyester usinga number 22 wire wound coating rod and the coatings allowed to air dryfor 30 minutes. The coated samples were then exposed to a 150 watttungsten spotlight at a distance of 10 cm from the sample surface. Thetime required to produce a non-tacky surface for each sample is given inTable I.

                  TABLE I                                                         ______________________________________                                                                    Time to                                                 Counterion of         produce                                           Ex.   (η.sup.6 -mesitylene)(η.sup.5 -cyclopentadienyl)-                                           non-tacky                                         No.   iron(1+)              surface                                           ______________________________________                                        1     SbF.sub.6.sup.-       30 sec                                            2     AsF.sub.6.sup.-       45 sec                                            3     PF.sub.6.sup.-        120 sec                                           4     BF.sub.4.sup.-        greater than 30                                                               min.sup.(a)                                       ______________________________________                                         .sup.(a) becomes nontacky after heating at 100° C. for 60 min.    

EXAMPLES 5-7

Coatings were prepared as described in Examples 1-4 using a catalyst thehexafluorophosphate salts of respectively, (Example 5) (η⁶-naphthalene)(η⁵ -cyclopentadienyl)iron(1+). (Example 6) (η⁶-chrysene)(n5-cyclopentadienyl)iron(1+), and (Example 7) (η⁶-pyrene)(05-cyclopentadienyl)iron(1+). (These salts were preparedaccording to the procedure described in J. Organometal. Chem. 101, 221(1975)). Samples of each coating (labeled (b)) were exposed to theoutput of the 150 watt tungsten lamp as described in Examples 1-4 andother samples of the coatings (labeled (c)) were exposed to the outputof the 150 watt tungsten lamp that passed through a light filter thatremoved 99% of the radiation below 440 nm. The time to produce anon-tacky coating for each sample is recorded in Table II.

                  TABLE II                                                        ______________________________________                                                          Time to produce                                                               non-tacky surface                                           Ex.   Catalyst          (b)       (c)                                         No.   hexafluorophosphate salt of:                                                                    no filter 440 nm filter                               ______________________________________                                        5     (η.sup.6 -naphthalene)(η.sup.5 -cyclo-                                                  30 sec    60 sec                                            pentadienyl)iron(1+)                                                    6     (η.sup.6 -chrysene)(η.sup.5 -cyclopenta-                                                30 sec    60 sec                                            dienyl)iron(1+)                                                         7     (η.sup.6 -pyrene)(η.sup.5 -cyclopenta-                                                  15 sec    30 sec                                            dienyl)iron(1+)                                                         ______________________________________                                    

EXAMPLES 8 and 9

The procedure of Example 5-7 was repeated using as catalyst thehexafluorophosphate salt and the hexafluoroantimonate salt of (η⁶-fluorene)(η⁵ -cyclopentadienyl)iron(1+). The time required to produce anon-tacky surface with the hexafluorophosphate salt was 60 seconds forexposures without the filter and 120 seconds with the filter. With thehexafluoroantimonate salt, exposures to produce a non-tacky surface were30 and 60 seconds respectively.

The (η⁶ -fluorene)(η⁵ -cyclopentadienyl)iron(1+) salts were prepared asdescribed in Hendrickson, Ph.D. thesis, Univ. of Florida (1978).

EXAMPLES 10-15

Coating solutions were prepared by mixing 10 parts of stock solution, 2parts of acetone and 0.1 part of each of the various organometalliccomplex salts shown in Table III. Each solution was coated and dried asdescribed in Examples 1-4 and exposed as described in Examples 5-7. Thetime required to produce a non-tacky surface for each is given in TableIII.

                  TABLE III                                                       ______________________________________                                                             Time to                                                                       produce non-tacky                                                             surface sec.                                             Ex.                        no       440 nm                                    No.  Catalyst.sup.(d),(e)  filter   filter                                    ______________________________________                                        10   [(η.sup.6 -1,2,3,4,4a,9a)-9-(4-methylphenyl-                                                    30       90                                             methylidene)fluorene]-                                                        (η.sup.5 -cyclopentadienyl)iron(1+)                                  11   [(η.sup.6 -1,2,3,4,4a,9a)-9-(4-methoxy-                                                         15       60                                             phenylmethylidene)fluorene]-                                                  (η.sup.5 -cyclopentadienyl)iron(1+)                                  12   [(η.sup.6 -1,2,3,4,4a,9a)-9-(2,4-dimethoxy-                                                     30       60                                             phenylmethylidene)fluorene]-                                                  (η.sup.5 -cyclopentadienyl)iron(1+)                                  13   [(η.sup.6 -1,2,3,4,4a,9a)-9-(3,4-dimethoxy-                                                     15       90                                             phenylmethylidene)fluorene]-                                                  (η.sup.5 -cyclopentadienyl)iron(1+)(*)                               14   [(η.sup.6 -1,2,3,4,4a,9a)-9-(3-phenyl-2-                                                        60       90                                             propenylidene(fluorene]-                                                      (η.sup.5 -cyclopentadienyl)iron(1+)                                  15   [(η.sup.6 -1,2,3,4,4a,9a)-9-(4-N,N-dimethyl-                                                    45       120                                            aminophenylmethylidene)fluorene]-                                             (η.sup.5 -cyclopentadienyl)iron(1+)                                  ______________________________________                                         .sup.(d) All counterions are hexafluorophosphate                              .sup.(e) Prepared by first condensing the corresponding aldehyde (i.e.,       4methylbenzaldehyde, 4methoxybenzaldehyde, 2,4dimethoxybenzaldehyde,          3,4dimethoxybenzaldehyde, cinnamaldehyde, and                                 4N,N-dimethylaminobenzaldehyde) with                                          (η.sup.6fluorene)(η.sup.5cyclopentadienyl)iron(1+)                    hexafluorophosphate (prepared in Example 8) using a catalytic amount of       potassium hydroxide in aqueous ethanol under nitrogen.                        ##STR3##                                                                 

EXAMPLE 16

A coating solution, prepared by mixing 10 parts of stock solution, 1part of acetonitrile and 0.1 part of (η⁶ toluene)(η⁵cyclopentadienyl)iron(1+) hexafluorophosphate, (prepared as described inthe previously cited Ph.D. Thesis of W. A. Hendrickson), was coated anddried as described in Examples 1-4. On exposure of the dried coating toa 150 watt tungsten spotlight at 10 cm, a non-tacky surface was obtainedin 60 seconds. Only 30 seconds were required to produce a non-tackysurface when the coating was exposed to the output of a 275 watt G.E.sunlamp at 10 cm.

EXAMPLES 17 AND 18

Example 16 was repeated using poly(η⁶ -styrene)(η⁵-cyclopentadienyl)iron(1+) hexafluorophosphate or poly(η⁶-styrene)tricarbonylmanganese(1+) hexafluoroarsenate in place of (η⁶-toluene)(η⁵ -cyclopentadienyl)iron(1+) hexafluorophosphate. Exposuretimes were 120 seconds and 45 seconds to produce a non-tacky coatingusing the 150 watt tungsten spotlight and the 275 watt sunlamprespectively.

The polystyrene iron complex was prepared as described in thebefore-mentioned Ph.D. thesis and the polystyrene manganese complex wasprepared as described in J. Chem. Soc. (Chem. Comm.) 688 (1975) usingpolystyrene having a number average molecular weight of 22,000 in placeof mesitylene or toluene, respectively. The iron complex obtained hadapproximately one (η⁵ -cyclopentadienyl)iron(1+) unit per eight stryreneunits and the manganese complex obtained had approximately onetricarbonylmanganese(1+) unit per three styrene units.

EXAMPLES 19-51

Polymerizable solutions were prepared as described in previous examplesusing the polymerizable compositions and the organometallic salts listedin Table IV. Each solution was coated onto primed polyester film and thecoating dried as previously described, and exposed to polymerizingconditions as shown in Table IV. The time required to obtain a tack-freecoating for each is given in Table IV.

                  TABLE IV                                                        ______________________________________                                        Ex.                       Time of   Oven                                      no.  Ionic organometallic complex salt.sup.(f)                                                          sunlamp.sup.(g)                                                                         at 75° C.                          ______________________________________                                        19   .sup.(h) [(η.sup.6 -1,2,3,4,4a,9a)(η.sup.6 -                                               15 sec                                                   5,6,7,8,8a,5a)fluorene]bis(η.sup.5 -                                      cyclopentadienyl)diiron(2+)                                                   hexafluorophosphate                                                      20   .sup.(i) bis(η.sup.6 -mesitylene)iron(2+)                                                      greater                                                  hexafluorophosphate  than                                                                          30 min                                              21   .sup.(i) bis(η.sup.6 -mesitylene)iron(2+)                                                      greater                                                  hexafluoroarsenate   than                                                                          30 min                                              22   .sup.(j) bis(η.sup.6 -mesitylene)iron(2+)                                                       5 sec    10 min                                         hexafluoroantimonate                                                     23   .sup.(k) bis(η.sup.6 -hexamethylbenzene)cobalt                                                 10 sec    10 min                                         (2+) hexafluoroantimonate/hydrox-                                             ypentafluoroantimonate                                                   24   .sup.(l) bis(η.sup.6 -benzene)chromium(1+)                                                     20 sec                                                   hexafluoroantimonate                                                     25   .sup.(m) (η.sup.3 -allyl)(η.sup.5 -methycyclopenta-                                        15 min                                                   dienyldicarbonylmanganese(1+)                                                 hexafluoroarsenate                                                       26   .sup.(n) (η.sup.3 allyl)(η.sup.5 -methylcyclopenta-                                        30 min                                                   dienyldicarbonylmanganese(1+)                                                 hexafluorophosphate                                                      27   .sup.(n) (η.sup.5 -cyclohexadienyl)tricarbonyl-                                                120 sec   30 min                                         iron(1+) hexafluoroarsenate                                              28   .sup.(o) (η.sup.7 -cycloheptatrienyl)tricarbonyl-                                              15 min                                                   chromium(1+) hexafluorophosphate                                         29   .sup.(o) (η.sup.7 -cycloheptatrienyl)tricarbonyl-                                              30 sec                                                   chromium(1+) hexafluoroaresenate                                         30   .sup.(o) (η.sup.7 -cycloheptatrienyl)tricarbonyl-                                              15 sec                                                   chromium(1+) hexafluoroantimonate                                        31   .sup.(o) (η.sup.7 -cycloheptatrienyl)tricarbonyl-                                              30 sec                                                   molybdenum(1+) hexafluoroarsenate                                        32   .sup.(o) (η.sup.7 -cycloheptatrienyl)tricarbonyl-                                              15 min                                                   tungsten(1+) hexafluoroarsenate                                          33   .sup.(p) (η.sup.6 -toluene)tricarbonylmang-                                                    10 sec                                                   anese(1+) hexafluorophosphate                                            34   .sup.(p) (η.sup.6 -toluene)tricarbonylmang-                                                    15 sec                                                   anese(1+) hexafluoroarsenate                                             35   .sup.(q) (η.sup.6 -mesitylene)tricarbonylrhen-                                                 15 sec                                                   ium(1+) hexafluoroarsenate                                               36   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                240 sec                                                  triphenylphosphineiron(1+)                                                    hexafluorophosphate                                                      37   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                45 sec                                                   triphenylphosphineiron(1+)                                                    hexafluoroarsenate                                                       38   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                45 sec                                                   triphenylphosphineiron(1+)                                                    hexafluoroantimonate                                                     39   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                10 sec                                                   triphenylarsineiron(1+)                                                       hexafluoroarsenate                                                       40   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                 5 sec                                                   triphenylstibineiron(1+)                                                      hexafluoroantimonate                                                     41   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                10 sec                                                   triphenylstibineiron(1+)                                                      hexafluoroarsenate                                                       42   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                45 sec                                                   triphenylstibineiron(1+) hexafluoro-                                          phosphate                                                                43   .sup.(r) (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                greater                                                  triphenylstibineiron(1+) tetra-                                                                    than                                                     fluoroborate         60 min                                              44   .sup.(s) hexacarbonylrhenium(1+) hexa-                                                             20 sec                                                   fluoroantimonate/hydroxypenta-                                                fluoroantimonate                                                         45   .sup.(s) (η.sup.5 -cyclopentadienyl)tricarbonyl-                                               10 sec    30 min                                         iron(1+) hexafluoroantimonate                                            46   .sup.(t) (η.sup.5 -methylcyclopentadienyl)dicar-                                               30 sec    30 min                                         bonylnitrosylmanganese(1+) hexa-                                              fluorophosphate                                                          47   .sup.(t) (η.sup.5 -methylcyclopentadienyl)dicar-                                               15 sec    10 min                                         bonylnitrosylmanganese(1+) hexa-                                              fluoroantimonate                                                         48   .sup.(u) (η.sup.6 -aniline)(η.sup.5 -cyclopentadienyl)                                     15 sec                                                   iron(1+) hexafluoroarsenate                                              49   .sup.(u) (η.sup.6 -benzene)(η.sup.5 -cyclopentadienyl)                                     15 sec                                                   iron(1+) hexafluoroarsenate                                              50   .sup.(u) (η.sup.6 -carbazole)(η.sup.5 -cyclopenta-                                         15 sec                                                   dienyl)iron(1+) hexafluorophosphate                                      51   .sup.(v) [tris(η.sup.6 -benzenecobalt)dicar-                                                   120 sec                                                  bonyl](1+) hexafluoroantimonate                                          ______________________________________                                         .sup.(f) Coatings were made as described in previous examples using by        weight 0.1 part of the ionic complex in a mixture of 5 parts of vinyl         cyclohexene dioxide, 5 parts of                                               3,4epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1 part of       acetonitrile with the exception of Examples 19-21 in which 2 parts of         acetonitrile were used and Examples 22 and 51 in which 2 parts of             nitromethane were used.                                                       .sup.(g) Exposures were made using a 275 watt G. E. sunlamp at a distance     of 10 cm from the coating.                                               

Prepared in accordance with the procedure outlined in

(h) J. Organometallic Chem. 186, 265 (1980).

(i) J. Chem. Soc. (Chem. Comm.) 930 (1971).

(j) J. Organometallic Chem. 1, 307 (1964).

(k) Inorganic Synth. 6, 132 (1960).

(l) J. Organometallic Chem. 12, 18 (1968).

(m) J. Chem. Soc. (Chem. Comm.) 311 (1981).

(n) Angew. Chemie 72, 919 (1960).

(o) Inorg. Chem. 5, 1837 (1966).

(p) J. Chem. Soc. (Chem. Comm.) 688 (1975).

(q) Inorg. Chem. 1, 933 (1962).

(r) J. Inorg. Nucl. Chem. 1, 165 (1955) and Inorg. Chem. 5, 1177 (1966).

(s) J. Am. Chem. Soc. 99, 4726 (1977).

(t) Organometallic Synthesis, A. R. B. King, Academic Press, N.Y. 1965.

(u) W. A. Hendrickson, Ph.D. thesis, U. of Florida (1978).

(v) Gazz. Chim. Ital. 88, 1170 (1958).

EXAMPLES 52-63

To illustrate the range of concentrations of ionic salts oforganometallic complexes effective for catalyzing the polymerization ofcationically polymerizable compounds, solutions were prepared asdescribed previously consisting of stock solution, solvent, and 10.0 to0.01 percent by weight, based on total weight of stock solution, ofionic salt as shown in Table V. Each mixture was coated ontopoly(vinylidene chloride) primed polyester sheeting, dried, and exposedto the radiation of a 275 watt G. E. sunlamp at a distance of 10 cmuntil the coating was non-tacky to the touch. The results are given inTable V.

                  TABLE V                                                         ______________________________________                                                                    Conc.                                             Ex.                         of      Time of                                   no.  Ionic organometallic complex salt                                                                    salt    cure                                      ______________________________________                                        52   bis(η.sup.6 -mesitylene)iron(2+) hexafluoro-                                                     10.0     5 sec                                         antimonate                                                               53   bis(η.sup.6 -mesitylene)iron(2+) hexafluoro-                                                     1.0      5 sec                                         antimonate                                                               54   bis(η.sup.6 -mesitylene)iron(2+) hexafluoro-                                                     0.1     10 sec                                         antimonate                                                               55   bis(η.sup.6 -mesitylene)iron(2+) hexafluoro-                                                     0.01    greater                                        antimonate                     than                                                                          30 min                                    56   (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                           10.0     5 sec                                         triphenylstibineiron(1+)                                                      hexafluoroantimonate                                                     57   (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                           1.0      5 sec                                         triphenylstibineiron(1+) hexafluoro-                                          antimonate                                                               58   (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                           0.1     45 sec                                         triphenylstibineiron(1+) hexafluoro-                                          antimonate                                                               59   (η.sup.5 -cyclopentadienyl)dicarbonyl-                                                           0.01    greater                                        triphenylstibineiron(1+) hexafluoro-                                                                         than                                           antimonate                     30 min                                    60   (η.sup.6 -mesitylene)(η.sup.5 -cyclo-                                                        10.0     5 sec                                         pentadienyl)iron(1+) hexafluoroanti-                                          monate                                                                   61   (η.sup.6 -mesitylene)(η.sup.5 -cyclo-                                                        1.0      5 sec                                         pentadienyl)iron(1+) hexafluoroanti-                                          monate                                                                   62   (η.sup.6 -mesitylene)(η.sup.5 -cyclo-                                                        0.1     30 sec                                         pentadienyl)iron(1+) hexafluoroanti-                                          monate                                                                   63   (η .sup.6 -mesitylene)(η.sup.5 -cyclo-                                                       0.01    greater                                        pentadienyl)iron(1+) hexafluoroanti-                                                                         than                                           monate                         30 min                                    ______________________________________                                    

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodiment setforth herein.

We claim:
 1. A compound having the formula:

    [(L.sup.9)(L.sup.10)M.sup.p ].sup.+q Y.sub.n

wherein M^(p) represents a metal selected from Cr, Mo, W, Mn, Re, Fe,and Co; L⁹ represents 1 or 2 ligands contributing π-electrons that canbe the same or different ligand selected from substituted andunsubstituted (η³ -allyl, η⁵ -cyclopentadienyl, and η⁷-cycloheptatrienyl and substituted η⁶ -aromatic compounds selected fromη⁶ -benzene and substituted η⁶ -benzene compounds and compounds having 2to 4 fused rings each capable of contributing 3 to 12 π-electrons to thevalence shell of M^(p) ; L¹⁰ represents none or 1 to 3-ligandscontributing an even number of σ-electrons that can be the same ordifferent ligand selected from carbon monoxide or nitrosonium;with theproviso that the total electronic charge contributed to M^(p) by L⁹ andL¹⁰ plus the ionic charge on metal M^(p) results in a net residualpositive charge of q to the complex; and q is an integer having a valueof 1 or 2, the residual electrical charge of the complex cation; Y is ahalogen-containing complex anion selected from AsF₆ ⁻, SbF₆ ⁻ and SbF₅OH⁻ ; and n is an integer having a value of 1 or 2, the number ofcomplex anions required to neutralize the charge q on the complexcation.
 2. The compound according to claim 1 selected from the group(η⁵-cyclohexadienyl)tricarbonyliron(1+) hexafluoroarsenate, (η⁶-toluene)tricarbonylmanganese(1+) hexafluoroantimonate, (η⁶-mesitylene)tricarbonylrhenium(1+) hexafluoroantimonate, (η⁷-cycloheptatrienyl)tricarbonyltungsten(1+) hexafluoroarsenate, (η⁶-naphthalene)(η⁵ -cyclopentadienyl)iron(1+) hexafluoroantimonate, bis(η⁵-cyclopentadienyl)iron(1+) hexafluoroantimonate, bis(η⁶-benzene)chromium(1+) hexafluoroantimonate, bis(η⁶-hexamethylbenzene)cobalt(2+) hexafluoroarsenate, bis(η⁶-hexamethylbenzene)nickel(2+) hexafluoroantimonate, (η⁷-cycloheptatrienyl)(η⁵ -cyclopentadienyl)manganese(1+)hexafluoroarsenate, (η⁶ -mesitylene)(η⁵ -cyclopentadienyl)-iron(1+)hexafluoroantimonate, (η⁶ -mesitylene)(η⁵ -cyclopentadienyl)iron(1+)hexafluoroarsenate, bis(η⁶ -mesitylene)iron(2+) hexafluoroarsenate,bis(η⁶ -mesitylene)iron(2+) hexafluoroantimonte, bis(η⁶-hexamethylbenzene)cobalt(2+)hexafluoroantimonate/hydroxypentafluoroantimonte, bis(η⁶-benzene)chromium(1+) hexafluoroantimonate, (η³ -allyl)(η⁵-methycyclopentadienyldicarbonylmanganese(1+) hexafluoroarsenate, (η⁵-cyclohexadienyl)tricarbonyliron(1+) hexafluoroarsenate, (η⁷-cycloheptatrienyl)tricarbonylchromium(1+) hexafluoroarsenate, (η⁷-cycloheptatrienyl)tricarbonylchromium(1+) hexafluoroantimonate, (η⁷-cycloheptatrienyl)tricarboylmolybdenum(1+) hexafluoroarsenate, (η⁷-cycloheptatrienyl)tricarbonyltungsten(1+) hexafluoroarsenate, (η⁶-toluene)tricarbonylmanganese(1+) hexafluoroarsenate, (η⁶-mesitylene)tricarbonylrhenium(1+) hexafluoroarsenate, (η⁵-cyclopentadienyl)tricarbonyliron(1+) hexafluoroantimonate, (η⁵-methylcyclopentadienyl)dicarbonylnitrosylmanganese(1+)hexafluoroantimonate, (η⁶ -aniline)(η⁵ -cyclopentadienyl)iron(1+)hexafluoroarsenate, and (η⁶ -benzene)(η⁵ cyclopentadienyl)iron(1+)hexafluoroarsenate.
 3. The compound according to claim 2 which is (η⁶-mestiylene)(η⁵ -cyclopentadienyl)iron(1+) hexafluoroantimonate.
 4. Thecompound according to claim 2 which is bis(η⁶ -mesitylene)iron(2+)hexafluoroantimonate.
 5. The compound according to claim 2 which isbis(η⁶ -benzene)chromium(1+) hexafluoroantimonate.
 6. The compoundaccording to claim 2 which is (η⁵-methylcyclopentadienyl)dicarbonylnitrosylmanganese(1+)hexafluoroantimonate.
 7. The compound according to claim 1 wherein Y insaid formula is AsF₆ ⁻.
 8. The compound according to claim 1 wherein Yin said formula is SbF₆ ⁻.
 9. The compound according to claim 1 whereinY in said formula is SbF₅ OH⁻.
 10. The compound according to claim 1wherein L⁹ of said formula is at least one of η⁶ -m-xylene, η⁶-o-xylene, and η⁶ -p-xylene.
 11. The compound according to claim 1wherein L⁹ of said formula is η⁶ -isopropylbenzene.
 12. The compoundaccording to claim 1 wherein L⁹ of said formula is η⁶ -fluorene.
 13. Thecompound according to claim 1 wherein L⁹ of said formula is η⁶-naphthalene.
 14. The compound according to claim 1 wherein L⁹ of saidformula is η⁶ -pyrene.
 15. The compound according to claim 1 wherein L⁹of said formula is η⁶ -hexamethylenebenzene.
 16. The compound accordingto claim 1 wherein L⁹ of said formula is η⁶ -toluene.
 17. The compoundaccording to claim 1 which is bis(η⁵ -cyclopentadienyl)iron(1+)hexafluoroantimonate.
 18. The compound according to claim 1 wherein η⁶-o-xylene, and η⁶ -p-xylene,one L⁹ is η⁵ -cyclopentadienyl, L¹⁰ is notpresent, Mp is iron, q is 1, Y is SbF₆ ⁻, and n is 1.